Patent GB-636906-A (GB)
Title: Preparation of quaternising agents for heterocyclic nitrogenous cyanine dyes intermediates and photographic silver halide emulsions containing cyanine dyes quaternated with such agents
IPC: G03C1/28
Filed: 1947-07-03
Abstract: Dye intermediates of the general formula (1) <FORM:0636906/IV (b)/1> wherein R is H or an alkyl alkoxy, or anilino group or a halogen atom, R1 is H, a halogen atom, or an alkyl group, or R and R1 together form a methylenedioxy group, R2 is H or an alkyl group, X is O, S, or Se, n is 1 or 2, R3 is methyl, and Y represents the atoms to complete a 5- or 6-membered heterocyclic nitrogen nucleus, are prepared by heating the corresponding base with an ester of the general formula (2) <FORM:0636906/IV (b)/2> 2 - Methylbenzthiazole benzthiazolylmethyl - p - toluenesulphonate is prepared by heating together 2-methylbenzthiazole and 2-benzthiazolylmethyl-p-toluenesulphonate.  2-Methyl-5 : 6-methylenedioxybenzthiazole benzthiazolylmethyl - p - toluenesulphonate, 2 - methyl - 4 : 5 - diphenylthiazole benzthiazolylmethyl - p - toluenesulphonate, 2 - methyl - 6 - methoxybenzselenazole-b  - benzthiazolylethyl - p - toluenesulphonate, and 2 - methylbenzthiazole benzoxazolylmethyl - p - toluenesulphonate are similarly prepared.  Compounds of the general formula (2) are prepared by heating the corresponding o-aminophenol, o-aminothiophenol, or o-aminoselenophenol with glycollic or hydracrylic acid and reacting the product with p-toluenesulphonyl chloride.  2 - Benzthiazolylmethyl - p - toluenesulphonate is prepared by heating together 2-aminothiophenol and glycollic acid, pouring into water and treating with hydrogen peroxide to oxidize residual 2-aminothiophenol, and reacting a hot caustic soda solution of the product with p-toluenesulphonyl chloride.  b -2-Benzthiazolylethyl - p - toluenesulphonate, and 2 - benzoxazolylmethyl - p - toluenesulphonate are similarly prepared.  2 - Methylolbenzthiazole, 2 - methylolbenzoxazole, and 2 - b  - hydroxyethylbenzthiazole are obtained as intermediate products.ALSO:Methine dyes are prepared from intermediates of the general formula <FORM:0636906/IV (c)/1> wherein R is H or an alkyl, alkoxy or anilino group, or a halogen atom, R1 is H, a halogen atom, or an alkyl group, or R and R1 together form a methylenedioxy group, R2 is H or an alkyl group, X is O, S or Se, n is 1 or 2, R3 is methyl, and Y represents the atoms to complete a 5- or 6-membered heterocyclic nitrogen nucleus.  5 - [(3 - Benzthiazolylmethylbenzthiazolylidene - z) - ethylidene] - 3 - allylrhodanine is prepared by refluxing together 2-methyl-3-(2-benzthiazolylmethyl) - benzthiazole p - toluenesulphonate and 5-acetonilidomethylene-3-allylrhodanine in isopropyl alcohol containing triethylamine.  3 - Ethyl - 31 - benzthiazolylmethyl-5 : 6 : 51 : 61 - dimethylenedioxythiacarbocyanine iodide is prepared by heating together 2-b -acetanilidovinyl - 5 : 6 - methylenedioxybenzthiazole ethiodide and 2-methyl-5 : 6-methylenedioxy-3-(2-benzthiazolylmethyl)-benzthiazole p-toluenesulphonate in pyridine containing triethylamine.  3 - Ethyl - 31 - benzthiazolylmethyloxathiacarbocyanine iodide, 3 - benzthiazolylmethyl - 31-ethyl-5 : 6 - methylenedioxythiaoxacarbocyanine iodide, 4 - [(3 - benzthiazolylmethylbenzthiazolylidene-2)-ethylidene] - 2 - methyl - 5 - oxothiophene, 3-ethyl-31 - benzthiazolylmethyl - 5 : 6 - dimethyloxathiacarbocyanine iodide, 5 - [(3 - b  - benzthiazolylethylbenzthiazolylidene - 2) - ethylidene] - 3 - allylrhodanine, 3 - benzthiazolylmethyl - 11 - ethyl - 61-methylthia - 21 - cyanine iodide, 2 - p - dimethylaminostyryl - 3 - benzthiazolylmethylbenzthiazole, and 4 - [(3 - benzoxazolylmethylbenzthiazolylidene-2) - ethylidene] - 2 - methyl - 5 - oxothiophene are similarly prepared.  5 - [(b  - 3 - Ethylbenzthiazolylidene - 2) - a  - ethylethylidene] - 2 - (3 - benzthiazolylmethyl - 4 : 5 - diphenylthiazolylmethylene) - 3 - ethyl - 4 - oxotetrahydrothiazole iodide is prepared by refluxing together 2-b -methylmercaptovinylbenzthiazole ethiodide and 3-ethylrhodanine in isopropyl alcohol containing triethylamine, alkylating with dimethyl sulphate, and heating with 2-methyl-4 : 5-diphenyl-3-(2 - benzthiazolylmethyl) - thiazole p-toluenesulphonate.